Two recent studies investigated the rhodium-catalyzed C–H amidation of arenes using an N-methoxyamide as the amidating agent. Amidation reactions are useful in the synthesis and development of a wide variety of natural products, pharmaceutical compounds, and modern materials. This reaction results in ortho-amidated aromatic rings with wide functional group tolerance on both the N-methoxyamide and the arene, but its applicability is limited because it requires high reaction temperatures. The investigators have conducted a few mechanistic experiments and have proposed a possible catalytic cycle based on the results, but it is still unknown which step is rate determining. In addition, the intermediate structures have not been characterized. We model the reaction mechanism using electronic structure methods, including the identification of intermediates and activation barriers. Through this process, we also determine the function of the boric acid co-catalyst. The results lead to a better understanding of the energetics of the reaction and may suggest ways to alter reaction conditions in order to improve the applicability of the reaction.

Exploring the reaction mechanism of a Rh(III)-catalyzed amidation of arenes

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